Valence Tautomerism Induced Proton Coupled Electron Transfer:X−H Bond Oxidation with a Dinuclear Au(II) Hydroxide Complex
We report the preparation and characterization of the dinuclear AuII hydroxide complex AuII2(L)2(OH)2 (L=N,N′‐bis (2,6‐dimethyl) phenylformamidinate) and study its reactivity towards weak X−H bonds. Through the interplay of kinetic analysis and computational studies, we demonstrate that the oxidatio...
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description | We report the preparation and characterization of the dinuclear AuII hydroxide complex AuII2(L)2(OH)2 (L=N,N′‐bis (2,6‐dimethyl) phenylformamidinate) and study its reactivity towards weak X−H bonds. Through the interplay of kinetic analysis and computational studies, we demonstrate that the oxidation of cyclohexadiene follows a concerted proton‐coupled electron transfer (cPCET) mechanism, a rare type of reactivity for Au complexes. We find that the Au−Au σ‐bond undergoes polarization in the PCET event leading to an adjustment of oxidation levels for both Au centers prior to C(sp3)−H bond cleavage. We thus describe the oxidation event as a valence tautomerism‐induced PCET where the basicity of one reduced Au−OH unit provides a proton acceptor and the second more oxidized Au center serves as an electron acceptor. The coordination of these events allows for unprecedented radical‐type reactivity by a closed shell AuII complex.
Proton‐Coupled electron transfer (PCET)‐type reactivity of the dinuclear AuII hydroxide complex AuII2(L)2(OH)2 (L=N,N′‐bis (2,6‐dimethyl) phenylformamidinate) towards weak X−H bonds is reported. For C(sp3)−H oxidation Au−Au σ‐bond polarization leads to an adjustment of oxidation levels for both Au centers prior to the PCET event. The oxidation event for C(sp3)−H bonds is therefore described as a valence tautomerism induced PCET, where a basic reduced Au−OH unit serves as proton acceptor and the second more oxidized Au center as an electron acceptor. |
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Proton‐Coupled electron transfer (PCET)‐type reactivity of the dinuclear AuII hydroxide complex AuII2(L)2(OH)2 (L=N,N′‐bis (2,6‐dimethyl) phenylformamidinate) towards weak X−H bonds is reported. For C(sp3)−H oxidation Au−Au σ‐bond polarization leads to an adjustment of oxidation levels for both Au centers prior to the PCET event. The oxidation event for C(sp3)−H bonds is therefore described as a valence tautomerism induced PCET, where a basic reduced Au−OH unit serves as proton acceptor and the second more oxidized Au center as an electron acceptor.</description><identifier>ISSN: 0044-8249</identifier><identifier>EISSN: 1521-3757</identifier><identifier>DOI: 10.1002/ange.202318916</identifier><language>eng</language><publisher>Weinheim: Wiley Subscription Services, Inc</publisher><subject>Basicity ; Bonding strength ; Electron transfer ; Hydrogen bonds ; Hydroxides ; Oxidation ; Oxidoreductions ; Protons ; Tautomerism</subject><ispartof>Angewandte Chemie, 2024-04, Vol.136 (14), p.n/a</ispartof><rights>2024 The Authors. Angewandte Chemie published by Wiley-VCH GmbH</rights><rights>2024. This article is published under http://creativecommons.org/licenses/by/4.0/ (the “License”). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License.</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><cites>FETCH-LOGICAL-c1176-6fd038b1992bfa6fa4d45589621aaa2cf97053118857eb0902a4afa955cce7593</cites><orcidid>0000-0001-7377-6561 ; 0000-0002-1290-597X ; 0000-0002-3181-0175 ; 0000-0003-0957-4310</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fange.202318916$$EPDF$$P50$$Gwiley$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fange.202318916$$EHTML$$P50$$Gwiley$$Hfree_for_read</linktohtml><link.rule.ids>314,780,784,1416,27923,27924,45573,45574</link.rule.ids></links><search><creatorcontrib>Hess, Kristopher M.</creatorcontrib><creatorcontrib>Leach, Isaac F.</creatorcontrib><creatorcontrib>Wijtenhorst, Lisa</creatorcontrib><creatorcontrib>Lee, Hangyul</creatorcontrib><creatorcontrib>Klein, Johannes E. M. N.</creatorcontrib><title>Valence Tautomerism Induced Proton Coupled Electron Transfer:X−H Bond Oxidation with a Dinuclear Au(II) Hydroxide Complex</title><title>Angewandte Chemie</title><description>We report the preparation and characterization of the dinuclear AuII hydroxide complex AuII2(L)2(OH)2 (L=N,N′‐bis (2,6‐dimethyl) phenylformamidinate) and study its reactivity towards weak X−H bonds. Through the interplay of kinetic analysis and computational studies, we demonstrate that the oxidation of cyclohexadiene follows a concerted proton‐coupled electron transfer (cPCET) mechanism, a rare type of reactivity for Au complexes. We find that the Au−Au σ‐bond undergoes polarization in the PCET event leading to an adjustment of oxidation levels for both Au centers prior to C(sp3)−H bond cleavage. We thus describe the oxidation event as a valence tautomerism‐induced PCET where the basicity of one reduced Au−OH unit provides a proton acceptor and the second more oxidized Au center serves as an electron acceptor. The coordination of these events allows for unprecedented radical‐type reactivity by a closed shell AuII complex.
Proton‐Coupled electron transfer (PCET)‐type reactivity of the dinuclear AuII hydroxide complex AuII2(L)2(OH)2 (L=N,N′‐bis (2,6‐dimethyl) phenylformamidinate) towards weak X−H bonds is reported. For C(sp3)−H oxidation Au−Au σ‐bond polarization leads to an adjustment of oxidation levels for both Au centers prior to the PCET event. The oxidation event for C(sp3)−H bonds is therefore described as a valence tautomerism induced PCET, where a basic reduced Au−OH unit serves as proton acceptor and the second more oxidized Au center as an electron acceptor.</description><subject>Basicity</subject><subject>Bonding strength</subject><subject>Electron transfer</subject><subject>Hydrogen bonds</subject><subject>Hydroxides</subject><subject>Oxidation</subject><subject>Oxidoreductions</subject><subject>Protons</subject><subject>Tautomerism</subject><issn>0044-8249</issn><issn>1521-3757</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2024</creationdate><recordtype>article</recordtype><sourceid>24P</sourceid><sourceid>WIN</sourceid><recordid>eNqFkDFPwzAQhS0EEqWwMltigSHFduI4ZiultJEqylAQW3R1HEiV2MVJ1Fb8AWZ-Ir-ElCIYmU539733pIfQKSU9Sgi7BPOse4wwn0aShnuoQzmjni-42EcdQoLAi1ggD9FRVS0IISETsoPeHqHQRmk8g6a2pXZ5VeLYpI3SKb53trYGD2yzLNp1WGhVu_Ywc2CqTLurp8_3jzG-tibF03WeQp2331Vev2DAN7lpVKHB4X5zHscXeLxJnW0p3RqWreH6GB1kUFT65Gd20cPtcDYYe5PpKB70J56iVIRemKXEj-ZUSjbPIMwgSAPOIxkyCgBMZVIQ7lMaRVzoOZGEQQAZSM6V0oJLv4vOdr5LZ18bXdXJwjbOtJEJk8L3Ay6_qd6OUs5WldNZsnR5CW6TUJJsC062BSe_BbcCuROs8kJv_qGT_t1o-Kf9AlC1gH4</recordid><startdate>20240402</startdate><enddate>20240402</enddate><creator>Hess, Kristopher M.</creator><creator>Leach, Isaac F.</creator><creator>Wijtenhorst, Lisa</creator><creator>Lee, Hangyul</creator><creator>Klein, Johannes E. 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N.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Valence Tautomerism Induced Proton Coupled Electron Transfer:X−H Bond Oxidation with a Dinuclear Au(II) Hydroxide Complex</atitle><jtitle>Angewandte Chemie</jtitle><date>2024-04-02</date><risdate>2024</risdate><volume>136</volume><issue>14</issue><epage>n/a</epage><issn>0044-8249</issn><eissn>1521-3757</eissn><abstract>We report the preparation and characterization of the dinuclear AuII hydroxide complex AuII2(L)2(OH)2 (L=N,N′‐bis (2,6‐dimethyl) phenylformamidinate) and study its reactivity towards weak X−H bonds. Through the interplay of kinetic analysis and computational studies, we demonstrate that the oxidation of cyclohexadiene follows a concerted proton‐coupled electron transfer (cPCET) mechanism, a rare type of reactivity for Au complexes. We find that the Au−Au σ‐bond undergoes polarization in the PCET event leading to an adjustment of oxidation levels for both Au centers prior to C(sp3)−H bond cleavage. We thus describe the oxidation event as a valence tautomerism‐induced PCET where the basicity of one reduced Au−OH unit provides a proton acceptor and the second more oxidized Au center serves as an electron acceptor. The coordination of these events allows for unprecedented radical‐type reactivity by a closed shell AuII complex.
Proton‐Coupled electron transfer (PCET)‐type reactivity of the dinuclear AuII hydroxide complex AuII2(L)2(OH)2 (L=N,N′‐bis (2,6‐dimethyl) phenylformamidinate) towards weak X−H bonds is reported. For C(sp3)−H oxidation Au−Au σ‐bond polarization leads to an adjustment of oxidation levels for both Au centers prior to the PCET event. The oxidation event for C(sp3)−H bonds is therefore described as a valence tautomerism induced PCET, where a basic reduced Au−OH unit serves as proton acceptor and the second more oxidized Au center as an electron acceptor.</abstract><cop>Weinheim</cop><pub>Wiley Subscription Services, Inc</pub><doi>10.1002/ange.202318916</doi><tpages>9</tpages><orcidid>https://orcid.org/0000-0001-7377-6561</orcidid><orcidid>https://orcid.org/0000-0002-1290-597X</orcidid><orcidid>https://orcid.org/0000-0002-3181-0175</orcidid><orcidid>https://orcid.org/0000-0003-0957-4310</orcidid><oa>free_for_read</oa></addata></record> |
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title | Valence Tautomerism Induced Proton Coupled Electron Transfer:X−H Bond Oxidation with a Dinuclear Au(II) Hydroxide Complex |
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